Interpolymers of alpha-acyloxyacrylonitriles



Patented Sept. 23, 1952 INTERPOLYMERS oFt-AcYnoxYAcRYLo- NITRILES.

Joseph B. Dickey, Rochester; N1. Ya, assignor to; Eastman Kodak Company; Rochesten. .Na Yin a; corporation .oIi-New. J ersey No Drawing. Application August 18:19.50,

Serial No. 180,298

This invention relates tonew polymeric derivaitves of a-acyloxyacrylonitriles,methods for preparing these polymeric derivatives; and articles prepared therefrom.

The polymerization of a-acyloxyacrylonitriles, such as a-acetoxyacrylonitrile, alone orin the presence of other ethenoid monomers, has" been mentioned previously, although no methods whereby such polymerization couldhbe effected have beendescribed. (U. S. Patent 2,395,930, dated March 5, 1947' and" U. S. Patent 2,266,771, dated December 25, 1941.) In U. S. application Serial No. 777,378, filed October 1, 1947, now- U. S; Patent 2,537,881, issued January-9, 1951, Ihave shown a method of masspolymerizationor interpolymerization of a-acyloxyacrylonitriles; and the lactonization of-the polymers produced is described.

The instantapplication is a continuation-inpart of Serial No. 777,376.

An object of my invention is to provide new polymers comprisinga-acyloxyacrylonitriles; and in particular, a-acetoxyacrylonitrile. object is to provide a method for making such polymers. Still another object is to providearticles; such as films, fibers, tapes, sheets, etc., from these new interpolymers.

According to my invention, I interpolymerize an a-acyloxyacrylonitrile in the presence of -a vinyl monomer selected. from. the group consisting of acrylonitrile, styrene, isopropenyl acetate,

A further,

16 Claims. (CL. 2,60. 8.505-) alkyl acrylates containing from 1 to 4 carbon v atoms in the alkyl group,- and alkylww-methacrylatescontainingfrom 1 to-4,-carbon atoms in the alkyl group.. The interpolymers can be-prepared using only one vinyl monomer inaddition to the .a-acyloxyacrylonitrile, or from. 2 to.;3 of such wherein R. is an alkyl group, such as methyl, ethyl, n-propyl, and isopropyl (i. e. an alkyl group having the formulaCn-Hznn where n is:a.

positive integer from 1 to 3). Typical are aacetox-yacryltmitri-le,E or.- propionoxyacrylonitrile, a -n-butyroxyacrylonitrile, and oc-iSOblltYlOXY- acrylonitrile.

Typical. acrylatesand: a-methacrylates; which.

can beused in the. preparationof my new interpolymers include methyl acrylate, ethyl acrylate, -nm yl acrrlate. ,isopro yl acrylate, .n.-buty acrylate, isobutyl acrylate; secondary: butyl acrylate, methyl aemethacrylate, ethyllaz-meth'e acrylate, n-propyl a-methacrylate'. iSflllIflDYkl-ar methacrylate, n-butyl. aemethacrylate, secondary butyl a-methacrylate. isobutyl. a-methacrylat'e, etc.

Although the int rpolymerizati'on of 'a-acyloxyacrylom'triles wi vinyl monomers, other... than those set forth above, have beendescribed in my application Serial No. 77 I;3FT6, Iihave found that the vinyl monomers contemplatediby the present application provide especiallyusemll polymer products. 1

The 1 interpolymerization is ,acceleratedby heat or the well-knownpolymerization.catalysts. emplary of such catalysts are the organic peroxides (e. g; benzoyl, acetyl', acetyl benzoyl, lauroyl, oleoyl, triacetone, urea, etc. peroxidesi, inorganic peroxides, such as hydrogen peroxide, perborates (e. g. sodium andgpotassium borates), persulfates (e; g. sodium, potassium, and ammonium. persulfates-),,. etc... ...The: inter polymerization, canbe. carried out. bythe mass method, orv by the bead or emulsion methodin which water or some othermediumin'whi'ch'the monomers are. insoluble. is employedias1a 113,; persing, medium with or. without emulsiiying agents. The interpolymerization can also b'e' effected in the presence of a diluent. The diluent, if employed, is advantageously a solvent for the interpolymer. The diluent need not dissolve the interpolymer, but the monomers can be dissolved in. such a solvent, or a mixture of solvents, and the'interpolymer precipitated therefrom as it is formed. Alternatively, the new interpolymer of mrinvention can be prepared according to the-method described in I-Iagemeyer application Serial No. 180,297, filed herewith. The method described in the Hagemeyer application is espemany. useful in that it provides a method for obtainingproducts in pure form in the substantial absence of hydrolysis by-products.

The temperature at which the interpolymerizatio'nl'c'an be efiected can vary from room temperature (approximately 20 C'.) to the boiling point'j'of the monomers, or of the medium in whichthe polymerization is effected (e. g. 100 C.

for water). Advantageously, I can use a temperature of from'about 40-80. C.

Generally, I have found that the mostwusefnl- 75 to 95 per cent by weight of acrylonitrile have been found to be especially useful in that they provide synthetic fibers r yarns of high tenacity and good dyeability. Interpolymers containing 75 or a larger per cent of acrylonitrile can be dissolved in solvents which are known to dissolve polyacrylonitrile, and the solutions spun into a coagulating bath to give valuable synthetic fibers. Solvents useful for this purpose include N,N dimethylformamide, N,N dimethylacetamide, -y-butyrolactone, ethylene oarbamate, N- methyl-Z-pyrrolidone, etc. These viscous solutions containing from to 30 per cent by weight of the polymer can be extruded through an orifice into a coagulating bath containing a liquid, such as water, alcohol, etc., which is a. non-solvent for the polymer. The resulting filaments can be stretched or drafted from 100 to 1400 per cent, dried, relaxed, and extruded to give yarns having the properties mentioned above.

The following examples will serve to illustrate further the manner in which I prepare the interpolymers of my invention.

E iam ple 1.Interpolymer of c-acetoaryczcrylonitrile and styrene Example 2 .-Interpolymer of a-acetozcyacrylonitrile and acrylonitrile 10.8 g. of a-acetoxyacrylonitrile, 5.3 g. of acrylonitrile,-and 0.005 g. of benzoyl peroxide were heated at 40C. until polymerization was complete. A, yellowishpolymer which was insoluble in acetone was obtained.

Example 3.I11.terpolymer of a-acetoxyacrylonitrile and methyl a-methacrylate 110.8 g. of acetoxyacrylonitrile, 10.0 g. of methyl a-methacrylate, and 0.01 g. of benzoyl peroxide were-placed in a sealed tube under an atmosphere of nitrogen, and polymerized at 40 C. A

the above example, other copolymers can be prepared. Likewise, c-n-butyroxyacrylonitrile or a-isobutyroxyacrylonitrile can replace a-aceto-xyacrylonitrile in the above example.

Example 4.-Interpolymer of a-acetoxyacrylonitrz'le and isopropenyl acetate 10.8 g. of a-acetoxyacrylonitrile, 25.0 g. of isopropenyl acetate, and 0.5 g. of benzoyl peroxide were placed'in a sealed tube under an atmosphere ofnitrogen and polymerized at 80 C. The resulting yellowish-solid was dissolved in acetone, and then precipitated by pouring into water. The yellowish-White solid thus obtained was found to be suitable for molding, coating to form films, etc.

Example 5.Interp0lymer of a-propz'onoxyccry lom'trzle, styrene, and acrylonitrile 10.0 g. of a-propionoxyacrylonitrile, 10.0 g. of styrene, 10.0 g. of acrylonitrile, and 0.02 g. of-benzoyl peroxide were placed in a sealed-glass tube under an atmosphere of nitrogen and polymerized at C. When the polymerization was complete, the yellowish solid was removed, dissolved in acetone, and precipitated in water.

In another run, identical to that of the above example, the polymerization was stopped when only 20 to 30 per cent complete, and further polymerization inhibited by the addition of phenyl a-naphthylamine to the reaction product. The product was then poured into water, dissolved in acetone, and reprecipitated in water. When an acetone dope of this partially polymerized product was prepared, it was found to be suitable for spinning into fibers.

Several batches comprising a mixture of c-ac-- etoxy-acrylonitrile and styrene were heatedtogether in the presence of benzoyl peroxide (polymerization catalyst). The products were dis solved in acetone and precipitated in water as described in Example 1 above. The amounts (by weight) of a-acetoxyacrylonitrile, styrene, and benzoyl peroxide (except for Example 11 where none was used), time of heating, temperature, per cent of yield of polymer, and the appearance of the polymer products for each batch are given in the table below.

Table I.Interpolymers of aeacetomyacrylonitrile and styrene Monomer Mixture 0 Example Time Temp Per- 0 Per- A ear-an Percent Percent cent 1 Days cent pp 06 AAN Styrene 9 91 0.05 5 50 25 White, horny solid. 21 79 0.05 5 50 50 White, fibrous and rubbery. 26 74 0. 05 5 50 50 White, fibrous. 35 0.05 6 50 55 Curdy, white solid. 54 46 0.1 4 50 80 White, fibrous. 54 46 none 5 50 20 White, powder. 68 32 0.05 5 50 35 D0. 77 23 0. 05 5 50 25 D0. 81 19 0. 05 5 50 24 D0. 84 16 0.05 5 50 27 Do.

AAN=a-acetoxyacrylonitiile. =amount of catalyst based on combined weight of monomers.

yellowish copolymer which is soluble in acetone wasobtained. This copolymer was found to be weight of a-acetoxyacrylonitrile and 47 parts by particularly valuable for molding, coating into film s, and the like.

By substituting methyl aorylate, ethyl a-methacrylate, n-butyl a-methacrylate, or n-butyl Separate matches comprising 53 parts by weight of methyl-c-methacrylate wereheated at 50 C. in the presence of benzoyl peroxide and the polymer products dissolved in acetone and precipitated in water. The amounts of catalyst acrylate in molecularly equivalent amounts in' (based on combined weights of monomers), time of heatingryiel-d and ap' polymers Cat 15 g. portions of a monomeric mixture consisting of acrylonitrile and a-acetoxyacrylonitrile were dissolved in separate flasks containing 22.5 cc. of a solvent mixture of N,N-dimethylformamide and acetic acid (50/50 by volume) and 0.015 g. of benzoyl peroxide added to each of the flasks. The flasks were then heated at 60 C. for 48-72 hours until complete polymerization was assured, and the polymer precipitated, filtered, washed with water, and dried. The composition of the monomeric mixture, yield of polymer, per cent of a-acetoxyacrylonitrile in the polymer, per cent carbon in the polymer, and intrinsic viscosity of a solution of the polymer in pure N,N-dimethylformamide are given in the table below.

Monomer Mixture Polymer Yield Intrinsic Exam leNo.

.13 Pan Percent Pep Pep Viscosity cent cent cent cent AAN AN AAN C wherein R represents an alkyl group of from 1 to 3 carbon atoms, and from 95 to 5 per cent by weight of a monomer selected from the group consisting of styrene, isopropenyl acetate, acrylonitrile, alkyl acrylates containing from 1 to 4 carbon atoms in the alkyl group, and alkyl 0.- methacrylates containing from 1 to 4 carbon atoms in the alkyl group.

2. A resinous interpolymer comprising from 5 to 95 per cent by weight of a-acetoxyacrylonitrile and from 95 to 5 per cent by weight of acrylonitrile.

3. A resinous interpolymer comprising from 5 to per cent by weight of a-acetoxyacrylonitrile and from 95 to '70 per cent by weight of acrylonitrile.

4. A resinous interpolymer comprising from 5 to 95 per cent by weight of a-acetoxyacryloniwe and; ream-:-as teia er e eatywergnt styrene:

5, A resinous interpolymer comprising filonr:v

5 to 9-5"-per -cent*by-weight of a-acetoxyacrylonitrile and from. 95..to 5zper cent by weight of isopropenyl acetate? 6'. A resinousz:interpolymerscomprising fiom 5 to 95 per cent by weight of aeacetoxya'cryloni trile and from 95 to 5 per cent by weight of an alkyl acrylate containing from 1 to 4 carbon atoms in the alkyl group.

'7. A resinous interpolymer comprising from 5 to 95 per cent by weight of a-acetoxyacrylonltrile and from 95 to 5 per cent by weight of an alkyl a-methacrylate containing from 1 to 4 car bon atoms in the alkyl group.

8. A resinous interpolymer comprising from 5 to 95 per cent by weight of a-acetoxyacrylonitrile and from 95 to 5 per cent by weight of methyl a-methacrylate.

9. A process for preparing resinous interpolymers comprising heating in the presence of a peroxide polymerization catalyst from 5 to 95 parts by weight of an a-acyloxyacrylonitrile selected from those represented by the following general formula:

CHz--'C-CEN wherein R represents an alkyl group of from 1 to 3 carbon atoms, and from 95 to 5 parts by weight of a monomer selected from the group consisting of styrene, isopropenyl acetate, acryonitrile, alkyl acrylates containing from 1 to 4 carbon atoms in the alkyl group, and alkyl methacrylates containing from 1 to 4 carbon atoms in the alkyl group.

10. A process for preparing a resinous interpolymer comprising heating in the presence of a peroxide polymerization catalyst from 5 to 95 parts by weight of a-acetoxyacrylonitrile and from 95 to 5 parts by weight of acrylonitrile.

11. A process for preparing a resinous interpolymer comprising heating in the presence of a peroxide polymerization catalyst from 5 to 25 parts by weight of a-acetoxyacrylonitrile and from 95 to '75 parts by weight of acrylonitrile.

12. A process for preparing a resinous interpolymer comprising heating in the presence of a peroxide polymerization catalyst from 5 to 95 parts by weight of a-acetoxyacrylonitrile and from 95 to 5 parts by weight of styrene.

13. A process for preparing a resinous interpolymer comprising heating in the presence of a peroxide polymerization catalyst from 5 to 95 parts by weight of a-acetoxyacrylonitrile and from 95 to 5 parts by weight of isopropenyl acetate.

14. A process for preparing a resinous interpolymer comprising heating in the presence of a peroxide polymerization catalyst from 5 to 95 parts by weight of a-acetoxyacrylonitrile and parte by weight. of a-aeetoxyacrylonitrile and from 95 to 5 parts by weight of methyl -methecrylate. 1 v JOSEPH B. ,DICKEY.

REFERENCES CITED The following references are of record in the meet this patent:

3 1 UNITED sums PATENTS Number Name Date Johnston et a1 Mar. 5,1946 Wood Nov. 16, 1948 Dickey et a1. Mar. 8, 1949 Milone May 10, 1949 Dickey June 14, 1949 Dickey July 5, 1949 Dickey Jan. 9. 1951, 

1. A RESINOUS INTERPOLYMER COMPRISING FROM 5 TO 95 PER CENT BY WEIGHT OF AN A-ACYLOXYACRYLONITRILE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 